Azo dyestuffs



Patented a. 30,- 1934 x 1,978,783

UNITED sTA res PATENT OFFICE reverse Azo DYESTUFFS Miles Augustinus Dahlen, Wilmington, Del., as-

signor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. ApplicationDeeember 8, 1931,

' iSerial No."579,831

Q Claims. (o1; 260 76) ';This invention. relates to new chemical comare obtained by coupling the arylamides having pounds and processes for their manufacture. theformula: More particularly, theinvention relates to cheinical compounds containing 'theradical having the on I HO- 'followingprob'able formula: (3)

OH HO-- (which are described in my copending United States application Serial No. 438,913) with diazotized aromatic amines free from groups that L would render the compound water soluble, R, R, in which R and R represent benzene nuclei m in thefibove formula having the m which are free from substituent groups that slgmficance as formula The F pwould render the compound water-soluble and may be effected 1n the usual Ways m aqua which may contain halogen, alkyl and alkexy ous solution or in suspension or on the fiber. e5

3L9 (Risen Object ef the invention to produce new within the invention and how they may be presubstituents, and A;and A" represent alkylene While mefinvention is Susc,epti b1e of consid' groups containing at'least two carbon atoms, It ereble vanajtlon n mqdlficatlon m 11.18 manner especially contemplates azo dyes falling in the of its practical application, the following examabove class of commends Y ples will illustrate some of the products fallmg 0 heini'ea1 compoundslwhich 'are insoluble in wa- 'F h proportmns are glven m parts by ten Further objects are the production ornew W m pigments, new azo dyes which yield fast dyeing's j v Ewmpze and printings on the fiber and'in general toade; Vance the art. Other objects will appear herein- Wen boiled and dried cotton yarn is impreg 75 GONH-RO A Q 1yOR'el1NQO Twelve and seven-tenths parts of meta-chloroeiten v I e I, e s M nated with a solution containing per liter, 10 These objects are accomplished'by producing parts of Turkey red 10 parts of caustlc compounds having the following probable forof per cent strength and 5 parts of the E mule: 1 e (2 3 hydroxy naphthoyl) beta beta d1 1 I 3 (para chloro ortho amino phenoxy) di so N- Ne-Ar v Ar--N=N ethyl ether. The yarn thus treated is well wrung I i out, rinsed, and, without being dried, developed (2) 7 with a diazo solution of meta-chloro-aniline. The

diazo solution is prepared as follows:

aniline are dissolved in a mixture of 30 parts of 5 wherein Ar represents a carbocyclic or heterocycboiling i and 30 Parts P hydrochloric acid lic aromatic radical, preferably a member of the of strength- To thls Fmxture, Parts benzene, diphenyly naphthmene, anthracene er of cold water and parts of ice are then added.

v 410 carbazole' series, which contains no group or When the resultant mixture has cooled 90 45 the ter 3 1 1 1 a which may r parts of water with cold water, and 20 parts of groups would render the compound ater ciently, a, 0f 7.5 parts 0? SOdium soluble, such as, for example, the sulfonic or car 7 dissolved 30 P Water slowly F boxylic group; R and represent benzene When the diazotization 1s complete, the solution 1 1 are free from groups would iS a Volume equivalent t0 about may not contain substit'uents selected from" the Sodium acetate are added to neutralize the group halogen, alkyl, and alkoXy; A and A repre 81941 ysent alkyl ene groups containing atleasttwo car After the development of the color is complete, bon atoms. Rgand B may be alike or different. the yarn is removed from the developing bath Help .The same is true of A and A. These-compounds and washed with water and then with a soap so- 100 lution to remove excess arylamide and diazo-salt, as Well as to remove any developed dye not firmly fixed to the fiber.

By the above process, an orange dyeing of good fastness to light and hot soaping is obtained.

The dye probably possesses the following formula:

trite dissolved in 50 parts of water then introduced, the temperature being held below 10 C. during the diazotization. When the diazotization is complete, as shown by disappearance of free nitrous acid, the solution is diluted to a volume equivalent to 500 parts of water. Sodium acetate is then added until the solution is no Well boiled and dried cotton yarn impregnated with an aqueous grounding liquor containingin one liter 20 parts of Turkey red oil, 10 parts of, caustic, soda of. 40 per cen st en h a d. 5

parts of the di (2': 3 F hydroxy naphthoyl) beta beta di (para amino phenoxy) di ethyl ether. The treated yarn isthen wrungout as thoroughly as possible and developed in audiazo solution prepared as follows:

Sixteen and eight-tenth parts or anew-2- water containing 30 parts of hydrochlorieacid of 22 B. strength. The solution is cooled, 150 parts of ice added, and 7.2 parts of sodium nilonger acidwhen tested with Congo red papers. When coupling of the dye is complete in the developing bath, the yarn is removed and washed with water and then with soap solution to remove uncoupled diazo-salt and arylamide, and to remove any dye not thoroughly adhering to the fiber.

Bythis process. a dyeing of scarlet to red shade is obtained which showsexcellent fastness to light, soaping, boiling and chlorine. The dye probably possesses the following structure:

OCH:

The rollovdne tab e discloses. further combinations f. these new arylamides ofb etahydroxw naphthoic acid with arious suita l diazotized ar matic, ami es 011- 11G- oorrrr-O-oomomo O-EhGHaQONBQO amino-lanisole. are diss lved zoo pared boilin Coupled with the di-(2:3-hydroxy-naphthoyl)- Dmzo compound from deflvative' of Shade 3 1- 'min ;4-benz ylamino-2:5-diethoxy-henzene l3:fi'-di-(para-amino-phenoxy)-diethyl-ether Deep blue. 1 4 3-nitroe4-amino-to1uene; do Scarlet. 5' 2-nitro-4-chloro- Do. I v 6' 5-nitro-2-arnino-anisole. do Red.

' 7 Meta-ehloro-aniline o Orange.

8 4:4-.diamino-dipheny no do Bluish-black. 9 Alpha-naphthylamine do Bordeaux. 10 Alpha-amino-anthraquinone do Red. 11 2:5-diehl0ro-aniline d n Scarlet 12 Meta-chloro-aniline. B:B-di ortho-amino phenoxy) -diethyl-ethe Orange 13 5-nitro-2-amino-anisole do Bluish-red l4 4-nitro-2-amino-toluene do Scarlet 15 2-nitro-4-chloro-aniline I do .l Red. 16 2:5-dioh1oro'aniline (in 17 4-nitr0-2-amino-anis0le do 18 Dianisidlne .do 19 4vi -diamino-diphenylamine do 20 Ortho-ath oxy-benzene-azo-alpha-naphthylamine -do 21 3-nitr0-4-amino-t01uene-azo-cresidine .do 22, 1-amino-4-benzoylamino-2:5-dimethoxy-benzene... flzflg-lr ii-(para;ehloro-ortho-amino-phenoxy)-diethyl v e or. 23, 4-nitro-2-amino-anisole do Scarlet. 24 2:5-dich1oro-ani1ine; n ,7 V H Do. 25 5-nitro-2-amino-auiso1e o Red. 26 3-amino-carbazo1e. ..do Corinth 27 i-nitro-Z-amino-amsolm. #:fl di- (para-methyl-ortho-emino --phenexy) Scarlet.

diethyl ethe 28 3- nitro-4-arnino-toluene.. d Red. 29 -d ioh 1 -on mo fl W-d -(ort o* et o Y-paxe-aminomhenoxwca lett 3o dieithyl ether.

' 5-nitro-2-amino-aniso1e Red.

In general, azo dyes formed from p:p'-di (para-amino-phenoxy) -diethyl ether, ,3: ,5'-di- (ortho-amino-phenoxy) -diethyl ether, and 13:18- di (para chloro ortho amino phenoxy) diethyl ether are preferred. Dyes prepared as herein described from c:p'-di-(para-aminophenoxy)-diethyl ether derivatives are particularly advantageous from the standpoint of fastness to l 1 r; h l a 6 0H o-on -om-o-pm-om-o -o ONHQ The scarlet dyestuff of Example 27 exhibits good fastness to light. It has the following prob able constitution:

CHaO

O11 O-GHa-OHa-O-OHz-CHr-O CONH- I It will be understood that the scope of the invention is not limited by the particular examples set forth above. for example, bromine, may be substituted in the various aromatic nuclei of general Formula (2).

, Similarly, alkyl groups such as ethyl, isopropyl, etc., may be employed in place of methyl groups, and methoxy groups may be replaced by ethoxy or other acyclic ether groups.

Any other diazotizable aromatic amines containing no sulphonic or carboxylic groups or other groups that would render the dye water soluble may be coupled with beta-hydroxy-naphthoic acid arylamides of the type herein described. Products prepared in accordance with the ,present invention show unexpected and unpredictable improved properties over dyes and pigments Other halogens than chlorine,

prepared from other arylamides of beta-hydroxy-naphthoic acid, particularly in regard to fastness to washing, boiling, hot soaping, chlorine, light, etc. Moreover, the colors are most desirable from the standpoints of shade and brightness.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that I do not limit myself to the foregoing examples or description except as indicated in the following patent claims.

I t it HNOC I OCHs.

I claim:

1. The chemical compound having the general formula:

OH HO zene series containing no groups capable of rendering the compound water-soluble.

2. The chemical compound having the general formula:

.'ben-z'ene, diphenyl, naphthalene, anthracene, or carbazole series wherein Arrepresents an ar ree .ifr m any group ,cap

omatic radical which .at least two carbon atoms and X is a member of ble of rendering the -the'group consisting of halogen, :hydrogen, alkyl compound wa erso ub e, a d-B nd R epresent andalkoxy. radicalsofthe,benzene'seriescontaining,noggroups 'dfrhe newcompound having thegeneral forcapablezof renderi-riig-theicompound wateresoluble. tmula; f

wherein, Ar represents an aromatic radical of carbazole series which is free from any group capable of rendering-the compolundwater soluble, and X is a member of the group consisting of halogen, hydrogen, alkyl, and alkoxy.

7. The chemical compound having the general formula:

wherein Ar represents an aromatic radical of the benzene series which is free from any group capable of rendering the compound water-soluble, and R and R represent radicals of the benzene wherein, Ar represents an aromatic radical of the benzene or naphthalene series which is free from any group capable of rendering the compound water soluble and X is a member of the series containing no groups capable of rendering no the compound water-soluble. s

4. The chemical compound having the general formula:

wherein, Ar represents an aromatic radical which "group consisting of halogen, hydrogen, alkyl and.

is free from any group capable of rendering the alkoxy. compound water soluble,Aand A represent alky- 8. A chemical compound having the general lene groups containing at least two carbon atoms, formula: i I

-0H 110 a :fIlIZH4 O I32HV4 CONH i HNOG+ X is at-member 6f the groupconsistingof halogen, hydrogen, alkyl and alkoxy. -wherein'.Ar is an aromatic radical, said compound 5. Thechemical compound haying the general being obtain'able'by coupling a diazotized aroformula: i 1 i I N=N Ar Ar-Iifi V, OONH- OAO-AO l --HNoo j matic amine which is free from any group that would render the compound water soluble with the condensation product of 2-hydroXy-3-naphthoic, acid and p ,8 -di- (para-amino-phenoxy) diethyl ether;

wherein, Arrepresents an aromatic radical of the which is free from any group capable surrenderingthecompound water soluble,

A and A represent alkylene radicals containing 15D benzene, diphenyl, naphthalene, anthracene, or $0 9;The chemical compound-having thBrfOllOW- alkylene groups containing at least two carbon ing formula: 7 atoms.

.' 5 V N0: v v v v F i NO 0 omo r v r 0012a 10 N il r 85 GONHGOCHr-OHp-O-CHpGH O-QHNOC 9O 10. The chemical compound having the follow- 13. The process which comprises coupling a ing formula: diazotized aromatic amine, which is free from any on o-omorno OHlGH2-0 H0 GONHQ Qrmroo m0 l 11. The chemical compound having the following formula: group capable of rendering the resultant com- 5 a N 0: N O

011:0 00H. if i 40'. N .5

OH O-UHr-CHg-O-UHz-CHr-O no OONH HNOG 4 F.

50, 12. The process of producing new chemical pound water soluble, to a compound having the compounds which comprises coupling a diazotized following general formula:

OH H0 OONE-R-O-OHrOHs-O-OH -OH O--R'-HNOC aromatic amine which is free from any group wherein R and R are members of the benzene apa of e de i the c p nd water soluble series free from any group capable of rendering with a compound having the following general th dye ter soluble, formula: 14. The process which comprises coupling a diazotized aromatic amine, which is free from any 0H group capable of rendering the resultant com- 65'; pound water soluble, to a compound having the 14;)

'HNOG following general formula:

OH HO wherein R and R are members of the benzene wherein R and R are members of the benzene series containing no groups capable of rendering series free from any group capable of rendering the compound water soluble, and A and A" are the dye water soluble, and contain as substituents 15 6 ieveyse with a, diazotized aromatic amine which is free from any group capable of rendering the resultant compound water solulcrle.

' IG S'Fibe I 'S dyed with the dyestuff or 101mm 1." 1'7. Fibers dyed with the dyestufi 61 claim 2. i

18. Fibers dyed with the dyestufi of claim 3. 19. Fibers dyed with the dyesti fi of claim 4.

20. Fibers dyed with the dyestuiff of claim '7.

MILES Atidiis'rm s. DAHLEN 

